Competitive Diels-Alder reactions: cyclopentadiene and phospholes with butadiene

Diene-dienophile competing Diels-Alder reaction pathways of cyclopentadiene, 1H-, 2H- and 3H-phospholes with butadiene were explored at the B3LYP level using 6-31G(d) and 6-311+G(d,p) basis sets, and at the CCSD(T)/6-31G(d)//B3LYP/6-31G(d) level. Activation barriers show that cyclopentadiene favors a diene rather than a dienophile conformation. Pathways 1 and 2 (A and B) corresponding to butadiene as the diene and dienophile are predicted to be highly competitive in the case of 1H-phosphole. Secondary orbital interactions and the preferable bispericyclic nature of transition states are responsible for the stability of endo transition states. The study indicates that some of the transition states are bispericyclic and most of them are highly asynchronous. The reactions require a lower activation energy when the conversion of weak C=P to C-P occurs in the case of 2H- and 3H-phospholes. The high stability of the products resulting via path 1 can be attributed to the less strain in the bicyclo[4.3.0]nonadiene skeleton compared to the norbornene derivatives obtained from path 2. Activation and reaction energy values for these Diels-Alder reaction pathways are compared with the values reported for the [4+2] cyclodimerizations of each of the reactants to examine the likelihood of cyclodimerizations along these pathways.